Phenolic polymers made by aralkylation reactions

ABSTRACT

The present invention is directed to the formation of phenol alkylation polymers which release negligible phenol and formaldehyde emissions. The phenol aralkylation polymers of the present invention are derived from a phenolic monomer, at least one styrene derivative and an aryl diolefin. In addition to the phenolic monomer, styrene derivative and aryl diolefin, other reactants may be introduced to produce a product with particular properties.

This application is a divisional of application Ser. No. 08/501,516,filed Jul. 12, 1995, now U.S. Pat. No. 5,674,970.

This invention is directed to the formation of phenol aralkylationpolymers. The polymers produced in accordance with the present inventionrelease negligible phenol and formaldehyde emissions.

The polymer class within the scope of the present invention exhibitsunique compatibility with oils and alkyd coating systems as well as abroad range of polymer systems including urethanes, epoxies, acrylates,and others which show performance benefits from the additions ofphenolics and related aromatic components.

BACKGROUND OF THE INVENTION

It is well-established that substituted phenols such as butyl, amyl, andphenyl phenol react with formaldehyde to form modifiers for oil andalkyd varnishes. These modifiers have been used for many years.Phenolics are used to upgrade corrosion properties, improve adhesion,and improve substrate wetting. They can be "cooked" with various dryingoils or simply cold blended with oils or alkyds to produce sparvarnishes and metal primers. Although phenolics having some excellentperformance properties, such as excellent adhesion and good corrosionproperties, other properties are not so desirable. Phenolics have arelatively high viscosity which excludes their use in very low V.O.C.applications. Furthermore, phenolics turn dark in color upon aging whichlimits their use in some primer and most topcoat systems because ofcolor bleed-through. For instance, the use of phenolics in exteriormetal paints is limited to primers since the phenolics in such coatingsdarken (bleed through) with time, changing the color of light topcoats.Even when it is the primer that contains a phenolic, topcoats must bedark in color in order to not show bleed-through. Typically primers arered or gray. It is believed that darkening upon aging is caused by theformation of quinone methides in the phenolic polymer.

Phenolics having lower solution viscosities are desired in order toreduce solution viscosities in spar varnishes, bridge paints, porch anddeck enamels, and government specification paints.

Phenolics are generally used in conjunction with oils or alkyds forexterior primers. Due to environmental pressures and thecommercialization of new polymer systems such as urethanes, these typesof phenolics represent a shrinking market.

There has been very little change in the basic chemistry of the phenolicresins since their introduction over 70 years ago. Generally, phenolicresins for oils and alkyds are novolak polymers based on substitutedphenols. Originally, they were based on p-phenyl-phenol. This monomeroffered a preferred combination of oil solubility, color retention andcorrosion resistance. ##STR1##

Because of the high price and limited availability, polymers based onp-phenyl-phenol have been discontinued. A lower priced but lesseffective substitute is a polymer based on p-t-butyl phenol. ##STR2##

The physical properties of the p-t-butyl phenol resins are not as goodas those of the p-phenyl phenol based resins. The p-t-butyl phenolimparts good oil solubility and limits color body formation whencompared to other types of phenols. However, the methylene linkagesallow the formation of quinone methides. It is the presence of quinonemethides which is a major reason why the polymers will darken over time.It is believed that the phenyl group has better performance propertieswhen compared to an alkyl group.

Improvements in color and corrosion resistance can be made bysubstituting some bisphenol-A for p-t-butyl phenol. It is generallyaccepted that the isopropylidene linkage in the bisphenol-A moleculedecreases the tendency for quinone methide formation in phenolicpolymers. Unfortunately bisphenol-A, because of the two hydroxyl groups,has very poor solubility with oils and the common solvents used incoating formulations. Therefore, only modest modifications withbisphenol-A can be used for these polymers.

SUMMARY OF THE INVENTION

The present invention is directed to the formation of a class of phenolaralkylation polymers which exhibit improved oil solubility, improvedcompatibility with oil and alkyd-based polymers, as well as urethanes,epoxies and acrylates and a decreased tendency for color body formationand resultant darkening of coatings in which they are incorporated. Thepolymers can be made free of formaldehyde and phenol.

The present invention is directed to the formation of a phenolaralkylation polymer by aralkylating a phenolic monomer with at leastone styrene derivative to obtain an aralkylated phenol, then reactingthe aralkylated phenol with an aryl diolefin to obtain the phenolaralkylation polymer, with the aralkylated phenol joined to the aryldiolefin. Those skilled in the art will recognize the primary linkage isat the ortho position. This process produces a lower melting pointpolymer. ##STR3##

It will also be noted that the structures described in this textrepresent idealized average structures of the type thoseskilled-in-the-art use to represent phenolic-type polymers. Inactuality, such polymers are complex mixtures containing a range ofcompositions and which contain analogues of the structures depicted.

The present invention is also directed to the formation of a phenolaralkylation polymer by reacting a phenolic monomer with an aryldiolefin to obtain a phenol/aryl diolefin polymer and then aralkylatingthe phenol/aryl diolefin polymer with at least one styrene derivative toobtain phenol aralkylation polymer, with a portion of the phenoliccomponent joined to the aryl diolefin with a portion of the phenoliclinkages being p in orientation. This process produces a higher meltingpoint polymer. ##STR4##

It is to be understood that both the foregoing general description andthe following detailed description are exemplary and explanatory onlyand are not restrictive of the present invention as claimed.

DETAILED DESCRIPTION OF THE INVENTION

The present invention is directed to a class of phenol aralkylationpolymers which impart good oil solubility, limit color body formationand show a decreased tendency to darken over time. The phenolaralkylation polymers of the present invention evolve low phenol andformaldehyde emissions, and have excellent adhesion and corrosionproperties. Also, the products of the invention have high solubility innon-aromatic (Hazardous Air Pollutants ("HAP's") free) solvents.Further, the incorporation of an aryl diolefin into a phenolic polymerresults in the formation of polymer systems useful for incorporationwith many other polymers which include but are not limited to urethane,epoxy, and acrylate polymer systems. The increase in aromatic characterof the phenolic polymer results in an enhancement in their ranges ofcompatibility with the aforementioned polymer class, and also generallyleads to the enhancement of physical properties, adhesion, and barrierproperty performance.

The phenol aralkylation polymers of the present invention are derivedfrom a phenolic monomer, at least one styrene derivative and an aryldiolefin. In addition to the phenolic monomer, styrene derivative andaryl diolefin, other reactants may be introduced to produce a productwith particular properties.

The phenol aralkylation polymers are produced by a process having atleast two reaction steps. The order of the reaction of the threereactants is arranged to provide a phenol aralkylation polymer producthaving desired properties. For instance, at least one styrene derivativeis reacted with a phenolic monomer and then the product thereof isreacted with an aryl diolefin. Alternatively, a phenol monomer isreacted with an aryl diolefin, and then the product thereof is reactedwith at least one styrene derivative. Similarly, a portion of either thestyrene or aryl diolefin may be withheld for later reaction to achieve apredetermined polymer composition exhibiting a desired performancecharacteristic.

Reactants

The styrene derivatives may be any of the aryl substituted alkenehydrocarbons. Examples include styrene, α-methyl styrene, p-methylstyrene, p-t-butyl styrene, α-methyl-p-methyl styrene, β-methyl styrene,m-ethyl styrene, p-ethyl styrene, p-vinyl toluene, mixed vinyl toluenes,mixed t-butyl styrenes, mixed ethyl styrenes, mixed t-butyl styreneswith di-t-butyl styrenes, isopropenyl naphthalene, 2-methyl-1,1-diphenylpropene, 1-phenyl-1-pentene, and the like. Mixed styrene derivativesmeans a mixture of, for example,- p- and m- t-butyl styrenes. Thepreferred styrene derivatives are styrene and homologs of styrene of theformula ##STR5## Where Ar may be phenyl, naphthyl, biphenyl, orsubstituted phenyl, naphthyl, or biphenyl. In the later case, examplesof substitutions may be: ##STR6## Where R₄ and R₅ are independentlymethyl, ethyl, C₃ to C₁₀ alkyl, or a halogen. R₁, R₂ and R₃ areindependently hydrogen, an alkyl radical containing 1 to 5 carbon atoms,an aromatic or an alkyl aromatic. R₁, R₂ and R₃ can be otherfunctionalities such as a carboxyl as in the case of cinnamic acid.##STR7## Such systems are particularly valuable as a means ofintroducing carboxyl functionality ##STR8## Esters of styrenederivatives may also be used. R₁, R₂ and R₃ can be carboxyl (--CO₂ H) oralkoxy (--O--R) groups.

Preferably, the styrene derivative is styrene, α-methyl styrene,p-t-butyl styrene, m-ethyl styrene, p-ethyl styrene, p-vinyl toluene,mixed vinyl toluenes, mixed t-butyl styrenes, mixed ethyl styrenes,mixed t-butyl styrenes with di-t-butyl styrenes, or mixtures thereof.

The aryl diolefin can be represented by the following formula ##STR9##Wherein Ar is benzene, naphthalene, or biphenyl; R₁₀, R₁₁ and R₁₂independently are a hydrogen or an alkyl radical containing 1-5 carbonatoms. The orientation on the benzene ring is meta or para or mixturesthereof.

Possible substitutions for naphthalene include 1-3, 1-4, 1-5, 1-6, 1-7,1-8, 2-4, 2-5, 2-6, 2-7 or 2-8 and corresponding mixtures thereof.##STR10##

Possible substitutions for biphenyl include 1-3, 1-2', 1-1', 1-3', 2-3',and 3-3', and corresponding mixtures thereof. ##STR11## The aromaticnucleus may be substituted with various R groups, for example, methyland t-butyl.

Preferably the aryl diolefin is m- or p-diisopropenyl benzene (DIPB) ortheir m, p mixtures or mixed m/p divinylbenzene (DVB) of any of thecommercially available concentrations. m-DIPB is commercially availableat a 98% concentration. DVB is available at concentrations of, forexample, 53%, 62%, and 80%. DVB concentrations also containethyl-styrene (vinyl ethyl benzene). For instance, 80% DVB containsapproximately 20% ethyl styrene. Diols derived from DIPB such as m or pdiols of diisopropyl benzene are acceptable diolefin materials.

Diols derived from DIPB such as m or p diols of diisopropenyl benzeneare acceptable precurser materials for aryl diolefins since they can beconsidered blocked aryl diolefins. ##STR12##

All or a portion of the styrene derivatives or aryl diolefin may beproduced in situ by dehydration of methyl benzylic alcohols at reactiontemperatures above 100° C. and acidities sufficient to promotedehydration of the benzylic alcohols. The resulting styrene derivativeor aryl diolefin may be reacted with a phenolic monomer. Other means toproduce the reactants in situ that are within the skill of the art arewithin the scope of the present invention.

In the following set of reactions, it is shown that cumyl alcohol andα-methyl styrene both generate the same benzylic carbonium ion which isthe recognized intermediate required for generation the subjectstyrenated or divinylarylated phenolic polymers. It will be noted thatuse of the DIPB diols requires their incremental addition to a phenoliccontaining reaction mixture under conditions allowing the simultaneousremoval of the water produced from removal of the blocking group.##STR13##

Phenol Monomers

The phenolic monomers include phenols which contain at least two freereactive positions. For example, in the case of phenol and substitutedphenols, monomers contain at least two free reactive (ortho- orpara-positions). Examples include phenol itself, o-, p- and m-cresol,m-isopropyl phenol, 3,5-xylenol, 3,5-diisopropyl phenol and mixtures ofthese compounds. Specific classes include:

I. Phenolic monomers containing mononuclear phenolic substituents areshown by the formula: ##STR14##

Substitution may be ortho, meta, or para. R may be methyl, ethyl,isopropyl, n-propyl, t-butyl, isobutyl, n-butyl, 5-10 aliphaticsubstituents, phenyl, or a substituent derived from aralkylation withstyrene derivatives, e.g. styrene, p-methyl styrene, t-butyl styrene,mixed t-butyl styrenes, α-methyl styrene, and vinyl toluenes.

II. Polyhydroxy mononuclear and polynuclear phenolic monomers include:

(1) Hydroquinone, resorcinol, and catechol ##STR15##

(2) Alkyl or aralkyl, mono and disubstituted, hydroquinones ##STR16##wherein the substitutions of R₁ and R₂ on the ring include 2,3; 2,5; and2,6, and R₁ and R₂, independently, can be hydrogen, alkyl having 1-10carbon atoms, and aralkyl derived from styrenes as benzylic derivatives,as previously described. R₁ and R₂ can also be divinyl aromatics, whichcan give rise to chain extended systems, as taught herein, formonohydroxy phenolic monomers. The latter system advantageously requiresminimal incorporation of the dihydroxy monomer into the polymericproduct to achieve the desired high hydroxy functionality.

(3) Alkyl or aralkyl, monosubstituted resorcinol ##STR17## wherein R isin the 2, 4, or 5 position on the ring. R can be hydrogen, alkyl having1-10 carbon atoms, aralkyl derived from styrenes or benzylicderivatives, as previously described. R can be divinyl aromatic, whichcan give rise to chain extended systems, as taught for the monohydroxyphenolic monomers. Advantages of the latter systems include minimalincorporations of the subject monomer into an alkylation polymer toachieve the desired high hydroxy functionality.

Resorcinol can also be used in the disubstituted (alkyl or aralkyl) modeto produce lower functionality polymers and in combination withdifunctionally reactive monomers such as hydroquinone or monosubstitutedphenolics, as described herein.

(4) Alkyl or aralkyl, substituted catechol ##STR18## wherein thesubstitutions of R₁ and R₂ on the ring include 3,4 or 3,5 and wherein R₁and R₂, independently, can be hydrogen, alkyl having 1-10 carbon atoms,aralkyl derived from styrenes, or benzylic derivatives, as previouslydescribed. R₁ and R₂ can also be divinyl aromatics, which can give riseto chain-extended systems, as taught for the monohydroxy phenolics. Thelatter system also advantageously requires minimal incorporation of thedihydroxy monomer into the polymeric product to achieve the desired highhydroxy functionality.

(5) Alkyl or aralkyl, substituted polyhydroxy-polycyclic aromaticphenols. Examples include:

(a) Dihydroxynaphthalenes:

1,2; 1,3; 1,4; 1,5; 1,6; 1,7; 1,8; 2,3; 2,4; 2,5; 2,6; 2,7; 2,8.

(b) Dihydroxy derivatives of anthracene, phenanthracene, etc.

III. Polynuclear phenolic monomers include:

(1) Bisphenol A.

(2) Bisphenol F (a mixture of the following three molecules) ##STR19##

(3) Dihydroxy biphenyl-bisphenols derived from various means.

a) p,p'dihydroxybisphenyl.

b) disubstituted bisphenols derived from coupling of monosubstitutedalkyl phenolics by action of the enzymatic coupling of phenols (MeadProcess). The Mead Process is described in, for example, U.S. Pat. No.4,900,671 which is hereby incorporated by reference. ##STR20##

(4) Bisphenols or polymeric phenols coupled by aldehydes or ketones.##STR21##

The phenolic monomers may be employed as an initial phenolic monomer inthe reaction or may be employed as an additional phenolic monomer laterin the reaction. Whether the phenolic monomer is used at an initialstage or as an additional component depends on the particular reactionscheme employed as discussed later. Preferred initial phenolic monomersare phenol, bisphenol A and bisphenol F. Other preferred phenolicmonomers include p-t-butyl phenol, p-cumyl phenol, and p-octyl phenolwhich may be used as initial phenolic monomers or additional phenolicmonomers depending on the particular reaction scheme employed. Polymersproduced from the above monomers may also be used as the phenolicmonomer.

The aryl diolefin is used at a range of mole ratios relative to thephenoic component. The mole ratio of aryl diolefin to phenolic componentmay be from 0.2:1 to 1.1:1. The mole ratio>1 is used under circumstancesin which alkyl or aralkyl substituted phenolics are used and in whichhigh molecular weight product is desired. The lower end of the moleratio range is employed under circumstances where a low level of chainextension is required. The amount of aryl diolefin also depends on theamount of phenolic hydroxy substitution on the phenolic prepolymer ormonomer used. In the case of bisphenol A (a di-functional phenolicmonomer), less aryl diolefin may be required to give a desired degree ofphenolic functionality, because the monomer is higher in both molecularweight and functionality to start with. Similarly, a formaldehyde-linkedphenolic polymer can be further coupled with aryl diolefins to buildmolecular weight to desired levels. The converse is also true that anaralkylation polymer formed from phenolic and aryldiolefin componentscan be further increased in molecular weight by reaction withformaldehyde under the conditions used to prepare the aralkylationsystem. A preferred range of mole ratio is 0.4:1 to 0.8:1.

The degree of styrenation employed with this polymer class can alsovary. For the purposes of this invention, the degree of styrenation isdefined as the ratio between the moles of styrene derivatives used andthe molar equivalent of open reactive positions per phenolic monomericcomponent. The degree of styrenation is determined by subtracting thenumber of reactive positions used to couple with the aryl diolefin orother linking group from the total number of reactive positions permonomers. For example, phenol is considered to have 3 reactivepositions. If two phenol molecules are coupled with an aryl diolefin,two open positions remain per phenol ring. The theoretical mole ratiofor styrenation (moles of styrene per phenol molecule) is therefore 2.For the present invention, the effective range for styrenation is from20 to 100 percent of the theoretical mole ratio with the most effectiverange being 40 to 95 percent of theoretical.

Process

One embodiment of the present invention is directed to the formation ofa phenol aralkylation polymer by aralkylating a phenolic monomer with atleast one styrene derivative to obtain an aralkylated phenol, thenreacting the aralkylated phenol with an aryl diolefin to obtain thephenol aralkylation polymer, with the aralkylated phenol joined to thearyl diolefin. Those skilled in the art will recognize the primarylinkage is at the ortho position.

In accordance with this embodiment, a phenolic monomer and at least onestyrene derivative are reacted in the presence of an acid catalyst. ThepH of the reaction mixture is lowered by means of acid catalystaddition. Since the system is generally low in water content, theeffective acidity of the catalyst system is increased.

Acid catalysts which may be used include but are not limited to:

Alkylsulfonic acids--methane, ethane, and higher alkyl C₃ -C₁₀ ;

Arylsulfonic acids, toluene, xylene, and mixtures thereof; also,naphthalene sulfonic and aralkylated toluene, benzene, or naphthalenesulfonic acids containing C₁ -C₁₀ alkyl substituents;

Phenol sulfonic and sulfonated phenolic polymers which may includearalkylated phenolics;

Sulfuric acid;

Phosphoric acid;

Alkyl, aryl or aralkyl phosphate esters having at least one free acidicproton per molecule;

Hydrochloric acid;

Latent acid catalyst systems including organic acid chlorides,phosphorous oxychlorides, and the like;

Latent acid catalysts derived from amines and the above;

Oxalic acid, maleic acid and other strong organic diacids having initialpKa's<1.5; and

Halogenated organic acids such as chloroacetic and trifluoroacetic acid.

The amount of acid catalyst required depends on the effective acidityand type of catalyst selected. Strong acids such as sulfonic and methanesulfonic require quantities less than 0.20 percent based on the totalreactive charge providing that said reactants do not contain basicimpurities. It will be noted that dilute solutions of said acids can beused providing that provisions are made to remove water from thereaction mixture. Weaker acids require the use of larger quantities(quantities of catalyst) with those skilled in the art being familiarwith methods for optimization.

The temperature of the reaction depends on a number of factors and ispreferably between 120°-160° C. The temperature selected depends on thenature of the aralkylating agent and requires optimization for eachsystem. In some instances, high temperatures are desired to insureagainst o-aralkylation of the phenolics or in others lower temperaturesare desirable to minimize retroaralkenylation with the resultantformation of undesired arylolefin coupling products. In any case, thereaction time required can vary significantly, but is generally achievedin the 10-30 minute time frame at the average (140° C.) reactiontemperature. This combination of conditions can be applied to allcombinations of phenol, substituted phenols, and phenol aralkylationproducts with either styrene, its derivatives, or aryldiolefins. It isworth noting that the aralkylation reaction is stopped completely byneutralization of the acid catalyst, and that systems so stabilized canbe heated to temperatures in the 200°-250° C. range for substantialperiods without de-aralkylations or other similar decompositions.

The phenolic monomer is selected to provide an aralkylated phenol and ispreferably phenol, bisphenol A or bisphenol F. Additional phenolicmonomers may be added prior to reacting the aralkylated phenol with thearyl diolefin such as p-t-butyl phenol, p-cumyl phenol and p-octylphenol. It is within the skill of the art to determine what phenolicmonomers are appropriate to react with the styrene derivative to obtainan aralkylated phenol and what phenolic monomers may be added later tobuild the polymer.

The aralkylated phenol product is then reacted with an aryl diolefin toobtain the phenol aralkylation polymer, with the aralkylated phenoljoined to the aryl diolefin primarily at the o-position. The pH of thereaction mixture is lowered by means of acid catalyst addition. The samecatalysts can be considered for diolefin reaction with the styrenatedphenols as were used to promote the reaction of phenol or itsderivatives with arylolefins. Indeed, in practice of this invention, thesame catalyst system is normally used to conduct the divinylaromatic-phenolic polymerization reaction as was used for the precursorphenolic reactant styrenation.

After conducting the aralkylation reactions, the final product can beneutralized with caustic, potassium hydroxide, or generally any alkalinematerial.

As a non limiting example for illustrative purposes only, the reactionof α-methyl styrene with phenol is set forth below. ##STR22##

In a comparison with bisphenol A, the aralkylated phenol product ismissing a hydroxyl group and thus does not have the poor compatibilitywith oils or solvents that are exhibited by bisphenol A.

The aralkylated phenol is then reacted with m-diisopropenylbenzene.##STR23##

Since the para position on the phenol has already been aralkylated, theonly place for the aryl diolefin (DIPB) to react is at an orthoposition. Polymers produced by initially reacting phenol with a styrenederivative result in lower melting point polymers.

Another embodiment employing this reaction scheme initially reacts aphenolic monomer with two styrene derivatives. For example, bisphenol Ais reacted with t-butylstyrene and α-methyl styrene. ##STR24## Thestyryl substituted bisphenol A systems can be further reacted withdivinyl aromatics to achieve chain-extended polymer systems useful incoating and other applications. These systems have good solubility inmineral spirits.

Another embodiment of the present invention is directed to the formationof a phenol aralkylation polymer by reacting a phenolic monomer with anaryl diolefin to obtain a phenol/aryl diolefin polymer and thenaralkylating the phenol/aryl diolefin polymer with at least one styrenederivative to obtain the phenol aralkylation polymer, with the phenoljoined to the aryl diolefin, as those skilled in the art will recognize,primarily at the ortho and para positions.

In accordance with this embodiment, a phenol and an aryl diolefin arereacted to form a phenol/diolefin polymer. The pH of this reactionmixture is lowered by means of acid catalyst additions. The samecatalyst systems and processing conditions are required for theseembodiments as were described earlier for aralkylation of theunsubstituted phenolic systems using styrene or substituted styrenes.

The phenol/diolefin polymer is then aralkylated with a styrenederivative in the presence of an acid catalyst to obtain the phenolaralkylation polymer. The same acid catalysts can be considered forstyrene aralkylation of the above phenol aralkylation polymer as wereused to react the aryldiolefin with the phenolic reactant. Indeed, inpractice of this invention, the same catalyst is used to catalyze boththe styrene and diolefin reactions with phenol and its derivatives. Thefinal product can be neutralized with caustic, potassium hydroxide, oran amine or generally any alkaline material compatible in the system.

As a non limiting example for illustrative purposes only, the reactionof phenol with diisopropenyl benzene is set forth below. ##STR25## Itwill be noted that depending on the amount of diolefin, there will be apossibility of some ortho substitutions. However, it is recognized thatthe para substituted form will predominate due to stearic hindrance.

The phenol/diolefin polymer is then reacted with α-methyl-styrene.##STR26##

Polymers produced by initially reacting a phenol with an aryl diolefingenerally result in higher melting point polymers than those produced byreaction of the aryldiolefin with preformed para styrenated phenolics.

Another example employing this reaction scheme reacts phenol anddiisopropenylbenzene as above, and then further reaction with p-t-butylstyrene to provide a high melting point (95°-105° C. versus 35°-45° C.for similar p-styrenated phenolic based polymers), phenol aralkylationpolymer depicted below and having good mineral spirits solubility.##STR27##

The acid catalyst may be any effective acid catalyst and is preferablymethane sulfonic acid. However, the catalyst systems described earliermay be employed with advantage depending on the results desired. It willbe noted that under conditions when neutralization of the catalyst withits removal by filtration is performed, that mineral acids may representthe most desired catalyst. For example, sulfuric or phosphoric acid arereadily removed as their sodium or potassium neutralization salts. Incontrast, under conditions where organic neutralization salts may be ofan advantage by allowing their retention in the final product as adissolved phase, the use of organic hydrophobic catalysts such as thealkyl naphthalene sulfonic acids and their amine neutralization productsmay be of an advantage. Amines can be selected from the group includingprimary, secondary and tertiary aliphatic (C₁ -C₁₀) and aralkyl aminesin which the amine substituents can be aromatic or benzylic incombination with aliphatic components (C₁ to C₁₀). A good neutralizingamine for purposes of these products would be diethyltertiary butylamine.

Another embodiment of the present invention reacts the phenolic monomerwith a portion of the aryl diolefin, and then reacts the remaining aryldiolefin after aralkylating the phenol with the styrene derivative.Polymers produced in this manner have advantages such as minimizing thepotential for gel formation.

The present invention produces a resin with low monomer content (<1percent and excellent yields without the use of formaldehyde. However,in either of the reaction schemes identified above, formaldehyde may beadded at any stage of the reaction to increase phenol monomer linking.An aralkylation reaction including the addition of formaldehyde isdemonstrated below.

First, phenol is aralkylated with α-methylstyrene. ##STR28##

Then the product is reacted with formaldehyde. ##STR29##

Then the product is reacted with divinyl benzene. ##STR30##

Other embodiments of the present invention include replacing up to 50%of the aryl diolefin with formaldehyde.

The following are more specific embodiments of the present invention.

A phenol aralkylation polymer is formed by reacting 1 mole of bisphenolA with from about 0.3 to 0.8 moles of an aryl diolefin to obtain abisphenol A/aryl diolefin polymer and then aralkylating the polymer withat least one styrene derivative selected from the group consisting ofp-t-butyl styrene, t-butyl styrene, vinyl toluene, α-methyl styrene, andstyrene wherein from 20 to 100 percent of the open reactive sites of thepolymer are occupied by styrene derived moieties.

In preparing this phenol aralkylation polymer, some or all of thestyrene derivatives may be reacted with the bisphenol A prior toreacting with the aryl diolefin providing that adequate open reactivepositions are retained, a mixture of an aryl diolefin and styrenederivatives may be coreacted with the bisphenol A and/or a portion ofthe bisphenol A may be replaced with t-butyl phenol.

A phenol aralkylation polymer is formed by reacting an aryl diolefinwith phenol at a mole ratio of aryl diolefin:phenol from about 0.4:1 to1.0:1 to form a phenol/aryl diolefin polymer and then reacting thepolymer with at least one styrene derivative selected from the groupconsisting of p-t-butyl styrene, t-butyl styrene, vinyl toluene,styrene, α-methyl styrene wherein from about 20 to 100 percent of theopen reactive sites of the polymer are occupied by styrene derivedmoieties.

In preparing this aralkylation polymer, some or all of the styrenederivatives may be reacted with the phenol prior to reacting with thearyl diolefin, formaldehyde may be reacted with the polymer to increasemolecular weight and reduce residual phenolic monomer levels, and/or aportion of the phenol may be replaced with t-butyl phenol.

The styrenated aralkylation phenolic polymers described herein can alsobe reacted with formaldehyde under basic conditions to generate resolesystems having unique solubilities and other related performancesadvantages. ##STR31## These latter polymer systems have utility in thepreparation of adhesives and other useful products. One such class ofadhesives described herein are cured with zinc complexes which requireonly the presence of phenolics with ortho methylols. Again, it must beemphasized that the systems described above are typical structures andthat in reality, the t-butylstyrene adducts as well as theformaldehyde-based methylol groups can occupy any of the available orthopositions during their reactions.

For polymers used as additives in air-dry paints, p-t-butyl-styrene or acombination of p-t-butyl-styrene with α-methyl-styrene or vinyl tolueneare preferred.

EXAMPLES

The invention will be further described by reference to the followingexamples. These examples should not be construed in any way as limitingthe invention.

The solubility of the following examples was determined using a 50 wt %solution of the phenol aralkylation polymer in a 5% n-butanol/mineralspirits solution.

In general, if a strong acid catalyst is employed, the type of equipmentthat can be used to produce the polymer is limited, for example, glasslined or stainless steel reactors should be used. Even very smallamounts of residual phenol will cause poor color retention and reducecompatibility with oils. Steam stripping or a TFE (thin film evaporator)may be required to get the monomer concentrations down to theappropriate levels. This problem was eliminated when bisphenol A wasused as the phenolic component. Analytical data have shown that low(less than 0.5 percent) levels of free phenol in the resultantaralkylations polymer can be attained in such polymer systems.

Example 1

A glass-lined reactor was purged with nitrogen. 188 g phenol and 0.6 gmethane sulfonic acid catalyst were charged to the reactor and themixture was heated to 120° C. An equal molar quantity (236 g) ofα-methyl styrene was slowly added while maintaining the temperature. Thereaction was exothermic and proceeded quickly. After this reaction hadtaken place, (130 g) diisopropenylbenzene (DIPB) was slowly added whilecontinuing to keep the temperature at 120° C. Since the para positionwas the primary site of aralkylation for the initial reaction step, themain position for the diisopropenylbenzene to react was at an orthoposition. This reaction was slower than the previous aralkylation.##STR32##

                  TABLE                                                           ______________________________________                                                            Commercial                                                                              Inventive                                                   CK-2500*                                                                              Mead Resin                                                                              Resin                                           ______________________________________                                        GPC                                                                           Mn            375       695       503                                         Mw            901       777       926                                         Polydispersity                                                                              2.4       1.1       1.8                                         Solubility in Mineral Spirits                                                               Limited   Limited   Excellent                                   Solution Viscosity                                                                          340 Cp.   225 Cp.   133 Cp.                                     Initial Color Off White Off White Off White                                   3 Month Color Beige     Off White Off White                                   ______________________________________                                         *Commercial G.P. product based on tbutyl phenol.                         

Initially the CK-2500 had the lowest color. When used to produce aresin, the CK-2500 tended to discolor more than the other materials. TheMead resin and the inventive resin each had higher molecular weight anda lower solution viscosity than the CK-2500. Low viscosity was adefinite advantage when formulating low V.O.C. products. Low viscositymeans less solvents required.

The compatibility with mineral spirits was best with the inventive resinshowing the utility of these systems in formulations requiring "HAP'sfree" solvents.

Example 2 ##STR33##

The reaction was run under a nitrogen atmosphere to minimize colorpickup. 456 g bisphenol A was melted in a reactor at 140° C. 1.3 g of(70 percent) methylene sulfonic acid was charged as a catalyst. 354 gα-methyl styrene was added over 30 minutes at 150°-160° C. and then heldfor 1/2 hour. 480 g t-butyl styrene was added over 30 minutes at150°-160° C. and held for 30 minutes. A low melting solid product wasproduced.

Example 3 ##STR34##

    ______________________________________                                        Charge Components   Component Weight (g)                                      ______________________________________                                        (1)     Bisphenol A     456                                                   (2)     o-xylene        200                                                   (3)     70% Methane sulfonic acid                                                                     0.46                                                  (4)     divinyl benzene (80%)                                                                         162                                                   (5)     α-methyl styrene                                                                        224                                                   (6)     t-butyl styrene 480                                                   ______________________________________                                    

The reaction was run under a nitrogen atmosphere to minimize colorpickup. Bisphenol A was melted in a reactor at 140° C. with 44% o-xylenebased on bisphenol A. 20% of the divinyl benzene was charged to thereactor. Then 0.1 wt % based on bisphenol A of 70% methylene sulfonicacid was charged as a catalyst. O-xylene was distilled until clear toremove any water in the system. The remaining divinyl benzene was addedover 20 minutes at 150°-160° C. and then held for 1/2 hour. α-Methylstyrene was added over 30 minutes at 150°-160° C. and held for 30minutes. t-Butyl styrene was added over 30 minutes at 150°-160° C. andheld for 30 minutes. The product was neutralized with 50% KOH and anexcess equal to 0.1% of bisphenol charge (azeotrope H₂ O) was added.After neutralization, the system was placed under vacuum and theo-xylene recovered from the system to produce a low melting solid (Mp45°-55° C.). Analysis showed the absence of arylolefin and diolefinmonomers. No detectable phenol or formaldehyde were found. The productexhibited excellent color, being a very light yellow. Pretreatment ofthe styrenes and aryldiolefins by passage through at alumina columnremoved traces of polymerization stabilizers (catechol andhydroquinone). Removal of these color-formers further improved the colorperformance of these polymers.

Example 4 ##STR35##

    ______________________________________                                        Charge Components  Component Weight (gms)                                     ______________________________________                                        (1)    Bisphenol A     212                                                    (2)    o-xylene        50                                                     (3)    70% Methane sulfonic acid                                                                     0.21                                                   (4)    divinyl benzene (80%)                                                                         101                                                    (5)    t-butyl styrene 298                                                    ______________________________________                                    

The reaction was run in a 1-liter resin kettle fitted with a stainlesssteel agitator. The reaction was run under a nitrogen atmosphere tominimize color pickup. Bisphenol A was melted in a reactor at 140° C.with 24% o-xylene based on bisphenol A. 20% of divinyl benzene wascharged to the reactor. Then 0.1 wt % based on bisphenol A of 70%methylene sulfonic acid was charged as a catalyst. The remaining divinylbenzene was added over 20 minutes at 150°-160° C. and then held for 1/2hour. Next, t-butyl styrene was added at a temperature of 150°-160° C.over a period of 30 minutes and then held at 150° C. for an additional30 minutes. At this point, o-xylene was removed from the reactor bydistillation. The resulting product was a solid (Mp 50°-60° C.).Analysis showed no trace of the olefin or diolefin monomers as well asphenol or formaldehyde.

Example 5 ##STR36##

The following reaction was run in a 1 liter reactor. The reaction wasrun under a nitrogen atmosphere to minimize color pickup. 319.2 gbisphenol A was melted in a reactor at 140° C. along with 50 g ofo-xylene. 0.3 g of 70% methane sulfonic acid catalyst and azeotropewater contained in the catalyst was charged using the o-xylenecosolvent. Charge 79 g of 80 percent divinyl benzene over 30 minutes at140°-150° C. The mixture was reacted for an additional 30 minutes at thereaction temperature and then neutralized at 150° C. using a portion of50 percent KOH equivalent to the methane sulfonic acid added. Thiseffective three functional polymer product is capable of furtherreaction with styrene derivatives.

Example 6 ##STR37##

The reaction was run under a nitrogen atmosphere to minimize colorpickup. 20 g of phenol was charged to a glass reactor fitted with amagnetic stirring bar and melt at 140° C. 0.02 g methane sulfonic acid(70 percent) was charged as a catalyst. 32 g diisopropenylbenzene wascharged over 10 minutes at 140° C. and heated for additional 20 minutesat 140° C. Next, 28 g of p-t-butyl styrene was charged to the reactionmixture over 20 minutes and heated for an additional 20 minutes at 140°C. The mixture was neutralized with an equivalent of diethylene triamineand then cast at room temperature from a 140° C. melt to give a solidresin.

Example 7 ##STR38##

The reaction was run under a nitrogen atmosphere to minimize colorpickup. 15 g of t-butyl phenol was charged into a glass reactor fittedwith a magnetic stirring bar and melted at 140° C. 0.015 g of 70 percentmethane sulfonic acid was charged. 10.3 g of 80 percent divinyl benzenewas then charged over 5 minutes at 140° C. The reaction was continued atthat temperature for an additional 10 minutes. Next, 10 g of p-t-butylstyrene was charged over 10 minutes and heated for an additional 10minutes at the 140° C. reaction temperature. The mixture was neutralizedwith an equivalent of diethylene triamine required for the TSA catalyst.The product was cast at room temperature from the 140° C. melt to give asolid resin having a mp--80°-90° C. The resulting resin was tested forsolubility in 5 percent butanol in mineral spirits and shown to besoluble in all proportions. Said phenolic resin was shown to contain nophenol or formaldehyde and was demonstrated to give excellent coatingfinishes when dissolved in a number of oil and alkyl-based vanishes.

Example 8 ##STR39##

The reaction was run under a nitrogen atmosphere to minimize colorpickup. 20 g of phenol was charged into a reactor and heated to 140° C.0.02 grams of methane sulfonic acid (70 percent) was added as acatalyst. 20 g of o-xylene was added as an azeotropic solvent. 25 gα-methyl styrene was added over 10 minutes at 140° C. The mixture washeated for an additional 20 minutes at 140° C. 6.87 g of 50 percentformaldehyde solution was slowly added allowing water and water ofcondensation produced by the reaction with the phenolic component to beremoved azeotropically over the addition period (20 minutes). After allformaldehyde was added, the mixture was allowed to continue heating for20 minutes at 140° C. Reactions of the aforementioned type were run witha Dean Stark decanter which was maintained at a "full" condition withthe selected azeotropic solvent. Finally, 17 g p-t-butylstyrene wascharged over 15 minutes at 140° C. with continued heating for anadditional 10 minutes after the addition was complete. At the end ofthis period an amount of diethylene triamine sufficient to neutralizethe MSA catalyst was added. The resulting neutralization product wascast onto a cold surface at 140° C. to give a flakable product having amelting point of 70° C. and a solubility at all proportions in 5 percentbutanol containing mineral spirits. The product performed well invarnish coatings. Various versions of the aforementioned polymer wereproduced in which a portion of the formaldehyde was replaced with aryldiolefins as the polymer chain extending agent. In these cases, infinitesolubility in pure mineral spirits was attained. Thus, the polymer ofthis invention has been demonstrated to be a unique means ofcompatibilizing phenolic polymers into highly nonpolar polymer solventsystems having a broad range of utility.

It will be apparent to those skilled in the art that variousmodifications and variations can be made in the compositions and methodsof the present invention without departing from the spirit or scope ofthe invention. Thus, it is intended that the present invention cover themodifications and variations of this invention provided they come withinthe scope of the appended claims and their equivalents.

What is claimed is:
 1. A phenol aralkylation polymer formed by reactingan aryl diolefin with phenol at a mole ratio of from about 0.4 to 1.0 toform a phenol/aryl diolefin polymer and then reacting the polymer withat least one styrene derivative selected from the group consisting ofp-t-butyl styrene, t-butyl styrene, vinyl toluene, styrene and a methylstyrene wherein from about 20 to 100 percent of the open reactive sitesof the polymer are occupied by styrene derived moieties.
 2. The phenolaralkylation polymer of claim 1 wherein some of the styrene derivativesare reacted with the phenol prior to reacting with the aryl diolefin. 3.The phenol aralkylation polymer of claim 1 wherein formaldehyde isreacted with the polymer to increase molecular weight, reduce residualphenol, or to add functional --CH₂ OH groups.
 4. The phenol aralkylationpolymer of claim 1 wherein a portion of the phenol is replaced witht-butyl phenol.
 5. A phenol aralkylation polymer formed by aralkylatingphenol with at least one styrene derivative selected from the groupconsisting of p-t butyl styrene, t-butyl styrene, vinyl toluene,α-methyl styrene, and styrene and then reacting the aralkylated phenolwith an aryl diolefin to obtain the phenol aralkylation polymer whereinfrom about 0.4 to 1.0 mole of said aryl diolefin is reacted per mole ofphenol and wherein from 20 to 100 percent of the open reactive sites ofthe polymer are occupied by styrene derived moieties.
 6. The phenolaralkylation polymer of claim 5 wherein a portion of the phenol isreplaced with t-butyl phenol.
 7. The phenol aralkylation polymer ofclaim 5 wherein formaldehyde is reacted with the polymer to increasemolecular weight, reduce residual phenol, or to add functional --CH₂ OHgroups.
 8. The phenol aralkylation polymer of claim 1 wherein the degreeof styrenation is in the range of 40 to 95%.
 9. The phenol aralkylationpolymer of claim 5 wherein the degree of styrenation is in the range of40 to 95%.